Imperial College London

ProfessorAnthonyKucernak

Faculty of Natural SciencesDepartment of Chemistry

Professor of Physical Chemistry
 
 
 
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Contact

 

+44 (0)20 7594 5831anthony Website

 
 
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Assistant

 

Mr Stuart Haylock +44 (0)20 7594 5717

 
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Location

 

433ChemistrySouth Kensington Campus

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Summary

 

Publications

Publication Type
Year
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200 results found

Rubio-Garcia J, Cui J, Parra-Puerto A, Kucernak Aet al., 2020, High energy density hydrogen/vanadium hybrid redox flow battery utilizing HCl as a supporting electrolyte for large scale energy storage applications, Energy Storage Materials, Vol: 31, Pages: 1-10, ISSN: 2405-8297

A high energy density Hydrogen/Vanadium (6 M HCl) system is demonstrated with increased vanadium concentration (2.5 M vs. 1 M), and standard cell potential (1.167 vs. 1.000 V) and high theoretical storage capacity (65 Wh L−1) compared to previous vanadium systems. The system is enabled through the development and use of HER/HOR catalysts with improved chemical stability towards the halogen-containing electrolyte within which the usual catalyst (Pt/C) is shown to quickly degrade during potential hold experiments. The implementation of an Ir/C catalyst at the negative side enables a system with high achievable energy density of 45 W h L−1 at 75 mA cm−2 associated with 67% electrolyte utilization. Based on such a promising performance, the system here presented could be a suitable solution for medium and large-scale energy storage with lower cost and volume footprint than existing batteries, particularly all-vanadium RFBs.

Journal article

Zhang G, Kucernak ARJ, 2020, The gas accessible membrane electrode (GAME): a versatile platform for elucidating electrocatalytic processes using real time and in situ hyphenated electrochemical techniques, ACS Catalysis, Vol: 10, Pages: 9684-9693, ISSN: 2155-5435

A gas accessible membrane electrode (GAME) is presented as a versatile tool for electrocatalysis research. With the use of an ultrathin and flat 12 μm thick porous electrode complimented by an efficient gas-circulating loop, the GAME facilitates rapid mass transport of reactants and products at the three-phase interface, enabling electrocatalytic processes to be investigated with fine kinetic details at high current densities (A cm–2) using only μg cm–2 of catalyst. The mass transport rate constant of the GAME is generally 1–2 orders of magnitude higher than those achieved using conventional techniques. The gas handling protocol ensures better utilization and fast switching of different gaseous environments within a few seconds, thereby reducing the use of gases and allowing for measurement of transient responses. This electrochemical configuration can be further coupled with a range of other analytical approaches, such as micro-/nanoelectrodes, mass spectrometry, photocatalysis, and Fourier-transform infrared spectroscopy for real-time/in situ electrochemical measurements, where reaction intermediates and products can be readily characterized. These innovative types of hyphenated platforms can be applied to study complex gas-to-fuel conversion processes (e.g., carbon dioxide electroreduction), in which multiple species need to be simultaneously identified and quantified to illustrate the dynamic product distribution. Moreover, the configuration can be possibly adapted for operando synchrotron-based X-ray characterization.

Journal article

Ma Y, Sikdar D, He Q, Kho D, Kucernak AR, Kornyshev AA, Edel JBet al., 2020, Self-assembling two-dimensional nanophotonic arrays for reflectivity-based sensing, Chemical Science, ISSN: 2041-6520

<p>We propose a nanoplasmonic platform that can be used for sensing trace levels of heavy metals in solutions <italic>via</italic> simple optical reflectivity measurements at the liquid–liquid interface.</p>

Journal article

Jackson C, Raymakers L, Mulder M, Kucernak Aet al., 2020, Poison mitigation strategies for the use of impure hydrogen in electrochemical hydrogen pumps and fuel cells, Journal of Power Sources, Vol: 472, Pages: 1-13, ISSN: 0378-7753

A new approach to mitigate against common poisons present in hydrogen for electrochemical hydrogen compressors and fuel cells is introduced. This approach uses the inclusion of ozone in the oxygen bleed as a poison mitigation strategy (online cleaning). This ozone treatment is also used to recover systems which have already been degraded by exposure to poisons (offline treatment). The different poisons studied are representative of products from a steam methane reformer (SMR), hydrogen contaminated by H2S, and an SMR feed contaminated with H2S. The efficacy of the cleaning methodology on the performance of an electrochemical hydrogen pump (EHP) and polymer electrolyte fuel cell are evaluated by comparing to the performance achieved when using pure hydrogen. Gas compositions containing ozone were more effective than O2 alone in cleaning poisons such as COad and Sad from the Pt/PtRu catalysts, thus, increasing the current densities and efficiencies of the EHP and polymer fuel cell. For the more severely poisoned streams, inclusion of ozone doubles the achievable current density. The mechanisms of catalyst regeneration using O2 and O2/O3 bleeds, following COad and Sad poisoning, involved both electrochemical and heterogeneous oxidation.

Journal article

Chakrabarti B, Rubio-Garcia J, Kalamaras E, Yufit V, Tariq F, Low CTJ, Kucernak A, Brandon Net al., 2020, Evaluation of a non-aqueous vanadium redox flow battery using a deep eutectic solvent and graphene-modified carbon electrodes via electrophoretic deposition, Batteries, Vol: 6, Pages: 1-20, ISSN: 2313-0105

Common issues aqueous-based vanadium redox flow batteries (VRFBs) face include low cell voltage due to water electrolysis side reactions and highly corrosive and environmentally unfriendly electrolytes (3 to 5 M sulfuric acid). Therefore, this investigation looks into the comparison of a highly conductive ionic liquid with a well-studied deep eutectic solvent (DES) as electrolytes for non-aqueous VRFBs. The latter solvent gives 50% higher efficiency and capacity utilization than the former. These figures of merit increase by 10% when nitrogen-doped graphene (N-G)-modified carbon papers, via a one-step binder-free electrophoretic deposition process, are used as electrodes. X-ray computed tomography confirms the enhancement of electrochemical surface area of the carbon electrodes due to N-G while electrochemical impedance spectra show the effect of its higher conductivity on improving RFB performance. Finally, potential strategies for the scaling-up of DES-based VRFBs using a simple economical model are also briefly discussed. From this study, it is deduced that more investigations on applying DESs as non-aqueous electrolytes to replace the commonly used acetonitrile may be a positive step forward because DESs are not only cheaper but also safer to handle, far less toxic, non-flammable, and less volatile than acetonitrile.

Journal article

Jackson C, Raymakers LFJM, Mulder MJJ, Kucernak ARJet al., 2020, Assessing electrocatalyst hydrogen activity and CO tolerance: comparison of performance obtained using the high mass transport ‘floating electrode’ technique and in electrochemical hydrogen pumps, Applied Catalysis B: Environmental, Vol: 268, Pages: 1-12, ISSN: 0926-3373

Current ex-situ electrochemical characterisation techniques for measuring the hydrogen reaction are insufficient to effectively characterise catalytic behaviour under CO containing environments. We show the high mass transport, floating electrode technique offers a solution as it adequately describes hydrogen oxidation (HOR) and evolution over a wide potential range, as needed for various electrochemical systems. The peak HOR mass activities measured on the floating electrode were 68–93 A.mgmetal-1 - significantly higher than achieved in an experimental setup of an electrochemical hydrogen pump (EHP, 6–12 A.mgmetal−1). This implies that the EHPs operate with a significant mass transport limitation. Additionally, poison tolerances of catalysts using low concentrations of 20 ppm CO produced transient responses over ca. 500 s which correctly followed the CO tolerances determined from EHPs (PtRu/C > Pt/C > PtNi/C). A model of the kinetic transient responses on the floating electrode is provided which aids in describing the catalytic behaviour in poisoned environments.

Journal article

Kucernak A, Mehmood A, Malko D, 2020, Establishing reactivity descriptors for platinum group metal (PGM)-free Fe-N-C catalysts for PEM fuel cells, Energy and Environmental Science, Vol: 13, Pages: 2480-2500, ISSN: 1754-5692

We report a comprehensive analysis of the catalytic oxygen reduction reaction (ORR) reactivity of four of today's most active benchmark platinum group metal-free (PGM-free) iron/nitrogen doped carbon electrocatalysts (Fe–N–Cs). Our analysis reaches far beyond previous such attempts in linking kinetic performance metrics, such as electrocatalytic mass-based and surface area-based catalytic activity with previously elusive kinetic metrics such as the active metal site density (SD) and the catalytic turnover frequency (TOF). Kinetic ORR activities, SD and TOF values were evaluated using in situ electrochemical NO2− reduction as well as an ex situ gaseous CO cryo chemisorption. Experimental ex situ and in situ Fe surface site densities displayed remarkable quantitative congruence. Plots of SD versus TOF (“reactivity maps”) are utilized as new analytical tools to deconvolute ORR reactivities and thus enabling rational catalyst developments. A microporous catalyst showed large SD values paired with low TOF, while mesoporous catalysts displayed the opposite. Trends in Fe surface site density were linked to molecular nitrogen and Fe moieties (D1 and D2 from 57Fe Mössbauer spectroscopy), from which pore locations of catalytically active D1 and D2 sites were established. This cross-laboratory analysis, its employed experimental practices and analytical methodologies are expected to serve as a widely accepted reference for future, knowledge-based research into improved PGM-free fuel cell cathode catalysts.

Journal article

Nguyen S, Millereux A, Pouyat A, Greenhalgh E, Shaffer M, Kucernak A, Linde Pet al., 2020, Structural power performance requirements for future aircraft integration, 22nd International Conference on Composite Materials 2019 (ICCM22), Publisher: Engineers Australia, Pages: 1-12

This paper investigates the use of structural power composites in Airbus A220-100 aircraft cabins by integrating floor panels with face sheets made of structural power composites to power the in-flight entertainment system. This application requires a minimum specific energy of 305 Wh/kg and a minimum specific power of 0.610 kW/kg. The static and dynamic loads for which the floor panels must be certified require an in-plane Young’s modulus of 50 GPa, a compressive strength of 225 MPa and a tensile strength of 119 MPa. Structural power composite floor panels are predicted to yield mass savings of 324 kg, annual cost savings of £85,000 per aircraft and annual reductions in CO2 and NOx emissions of 343 tonnes and 1.4 tonnes respectively. However, addressing challenges such as fire-resistance, long term cycling performance and public perception of structural power composites are necessary to enable widespread use of such materials on-board airliners.

Conference paper

Senokos E, Anthony D, Nguyen S, Kucernak A, Greenhalgh E, Shaffer Met al., 2020, Manganese dioxide decorated carbon aerogel/carbon fibre composite as a promising electrode for structural supercapacitors, 22nd International Conference on Composite Materials 2019 (ICCM22), Publisher: Engineers Australia, Pages: 1-8

Manganese dioxide electrochemically deposited onto carbon aerogel/carbon fibres (CAG/CF) shows a great potential as an electrode material in multifunctional structural supercapacitors. MnO₂ nanowires grown by a pulse potentiometric method provide a large enhancement in capacitive performance of the carbon electrodes and symmetric supercapacitor devices based on the hybrid material.

Conference paper

Johannisson W, Nguyen S, Lindbergh G, Zenkert D, Greenhalgh E, Shaffer M, Kucernak Aet al., 2020, A residual performance methodology to evaluate multifunctional systems, Multifunctional Materials, Vol: 3, ISSN: 2399-7532

The development of multifunctional materials and structures is receiving increasing interest for many applications and industries; it is a promising way to increase system-wide efficiency and improve the ability to meet environmental targets. However, quantifying the advantages of a multifunctional solution over monofunctional systems can be challenging. One approach is to calculate a reduction in mass, volume or other penalty function. Another approach is to use a multifunctional efficiency metric. However, either approach can lead to results that are unfamiliar or difficult to interpret and implement for an audience without a multifunctional materials or structures background.Instead, we introduce a comparative metric for multifunctional materials that correlates with familiar design parameters for monofunctional materials. This metric allows the potential benefits of the multifunctional system to be understood easily without needing a holistic viewpoint. The analysis is applied to two different examples of multifunctional systems; a structural battery and a structural supercapacitor, demonstrating the methodology and its potential for state-of-the-art structural power materials to offer a weight saving over conventional systems. This metric offers a new way to communicate research on structural power which could help identify and prioritise future research.

Journal article

Valkova M, Anthony DB, Kucernak ARJ, Shaffer MSP, Greenhalgh ESet al., 2020, Predicting the compaction of hybrid multilayer woven composite reinforcement stacks, Composites Part A: Applied Science and Manufacturing, Vol: 133, ISSN: 1359-835X

A meso-scale finite element modelling strategy was developed to investigate the effect of hybridisation on the compaction response of multilayer stacks combining glass and carbon dry woven fabrics. It is expected that the electrochemical-mechanical properties of emerging multifunctional hybrid composites are strongly dictated by the morphology of the compacted reinforcements, yet no investigations into their compressibility have been reported. Model predictions were evaluated against compressibility measurements for monolithic and hybrid fabric stacks. The ply offset had a major influence on the predicted internal morphologies and fibre content, contributing to experimental variability thereof. Optical microscopy and micro X-ray computed tomography imaging indicated greater likelihood of intermediate ply offsets in physical specimens, over limit case model idealisations. Compressibility was slightly reduced in the hybrid multilayer stacks studied in this work. The model outputs presented are being used to analyse the electrochemical-mechanical response of hybrid woven structural power composites.

Journal article

Jackson C, Smith GT, Mpofu N, Dawson JMS, Khoza T, September C, Taylor SM, Inwood DW, Leach AS, Kramer D, Russell AE, Kucernak ARJ, Levecque PBJet al., 2020, A quick and versatile one step metal–organic chemical deposition method for supported Pt and Pt-alloy catalysts, RSC Advances: an international journal to further the chemical sciences, Vol: 10, Pages: 19982-19996, ISSN: 2046-2069

A simple, modified Metal–Organic Chemical Deposition (MOCD) method for Pt, PtRu and PtCo nanoparticle deposition onto a variety of support materials, including C, SiC, B4C, LaB6, TiB2, TiN and a ceramic/carbon nanofiber, is described. Pt deposition using Pt(acac)2 as a precursor is shown to occur via a mixed solid/liquid/vapour precursor phase which results in a high Pt yield of 90–92% on the support material. Pt and Pt alloy nanoparticles range 1.5–6.2 nm, and are well dispersed on all support materials, in a one-step method, with a total catalyst preparation time of ∼10 hours (2.4–4× quicker than conventional methods). The MOCD preparation method includes moderate temperatures of 350 °C in a tubular furnace with an inert gas supply at 2 bar, a high pressure (2–4 bar) compared to typical MOCVD methods (∼0.02–10 mbar). Pt/C catalysts with Pt loadings of 20, 40 and 60 wt% were synthesised, physically characterised, electrochemically characterised and compared to commercial Pt/C catalysts. TEM, XRD and ex situ EXAFS show similar Pt particle sizes and Pt particle shape identifiers, namely the ratio of the third to first Pt coordination numbers modelled from ex situ EXAFS, between the MOCD prepared catalysts and commercial catalysts. Moreover, electrochemical characterisation of the Pt/C MOCD catalysts obtained ORR mass activities with a maximum of 428 A gPt−1 at 0.9 V, which has similar mass activities to the commercial catalysts (80–160% compared to the commercial Pt/C catalysts).

Journal article

Hakola L, Puerto AP, Vaari A, Maaninen T, Kucernak A, Viik S, Smolander Met al., 2020, Anode ink formulation for a fully printed flexible fuel cell stack, Flexible and Printed Electronics, Vol: 5, Pages: 1-12, ISSN: 2058-8585

In fuel cells the underlying reactions take place at the catalyst layers composed of materials favoring the desired electrochemical reactions. This paper introduces a formulation process for a catalyst inkjet ink used as an anode for a fully printed flexible fuel cell stack. The optimal ink formulation was 2.5 wt% of carbon–platinum–ruthenium mixture with 0.5% Nafion concentration in a diacetone alcohol solvent vehicle. The best jetting performance was achieved when 1 wt% binder was included in the ink formulation. Anodes with resistivity of approximately 0.1 Ω cm were inkjet printed, which is close to the commercial anode resistivity of 0.05 Ω cm. The anodes were used in fuel cell stacks that were prepared by utilizing only printing methods. The best five-cell-air-breathing stack showed an open circuit potential under H2/air conditions of 3.4 V. The peak power of this stack was 120 µW cm−2 at 1.75 V, with a resistance obtained from potentiostatic impedance analysis of 295 Ohm cm2. The printed electrodes showed a performance suitable for low-performance solutions, such as powering single-use sensors.

Journal article

Zalitis C, Kucernak A, Lin X, Sharman Jet al., 2020, Electrochemical measurement of intrinsic oxygen reduction reaction activity at high current densities as a function of particle size for Pt4–xCox/C (x = 0, 1, 3) catalysts, ACS Catalysis, Vol: 10, Pages: 4361-4376, ISSN: 2155-5435

While extensive literature shows Pt alloy catalysts are a more active substitute for pure Pt catalysts at 0.9 V, high activity is also needed at high current densities if they are to be adopted for fuel cell application. We use a newly developed electrochemical technique to compare the performance of a range of catalysts with initial composition Pt4–xCox/C of different particle sizes at high current densities (∼0.65 V vs RHE) as well as the typical ∼0.9 V vs RHE. Moving from 0.9 to 0.65 V, the current densities were found to increase by up to 80-fold for the Pt/C catalysts, with this factor decreasing as the amount of Co in the PtCo alloy increases. A kinetic model incorporating site blocking species at both high and low potentials has been used to explain this change. While the dealloyed catalysts were found to have a greater mass activity at low current densities (∼0.9 V vs RHE), they were no longer as active as 2.1 nm Pt particle catalyst at high current densities (∼0.65 V vs RHE). However, for equivalent particle sizes, the mass activity of the dealloyed Co-containing catalysts remains higher across the normal operating potentials of a fuel cell. Using this insight, we predict that at 0.65 V a catalyst composed of 3.8 nm CoPt@Pt1ML particles would give optimum mass activity performance. In addition, two peaks were observed during the cyclic voltammetry (CV) of the oxygen reduction reaction (ORR) on pure Pt nanoparticles in the hydrogen adsorption region (0–0.4 V vs RHE). These peaks are associated with surface sites with different reactivities toward the ORR.

Journal article

Ma Y, Sikdar D, Fedosyuk A, Velleman L, Klemme DJ, Oh S-H, Kucernak ARJ, Kornyshev AA, Edel JBet al., 2020, Electrotunable nanoplasmonics for amplified surface enhanced Raman spectroscopy, ACS Nano, Vol: 14, Pages: 328-336, ISSN: 1936-0851

Tuning the properties of optical metamaterials in real time is one of the grand challenges of photonics. Being able to do so will enable a new class of photonic materials for use in applications such as surface enhanced Raman spectroscopy and reflectors/absorbers. One strategy to achieving this goal is based on the electrovariable self-assembly and disassembly of two-dimensional nanoparticle arrays at a metal liquid interface. As expected the structure results in plasmonic coupling between NPs in the array but perhaps as importantly between the array and the metal surface. In such a system the density of the nanoparticle array can be controlled by the variation of electrode potential. Due to the additive effect, we show that less than 1 V variation of electrode potential can give rise to a dramatic simultaneous change in optical reflectivity from ~93 % to ~1 % and the amplification of the SERS signal by up to 5 orders of magnitude. The process allows for reversible tunability. These concepts are demonstrated in this manuscript, using a platform based on the voltage-controlled assembly of 40 nm Au-nanoparticle arrays at a TiN/Ag electrode in contact with an aqueous electrolyte. We show that all the physics underpinning the behaviour of this platform works precisely as suggested by the proposed theory, setting the electrochemical nanoplasmonics as a promising new direction in photonics research.

Journal article

Javier R-G, Kucernak A, Liu R, Chakrabarti Bet al., 2020, Hydrogen/functionalized benzoquinone for a high-performance regenerative fuel cell as a potential large-scale energy storage platform, Journal of Materials Chemistry A, Vol: 8, Pages: 3933-3941, ISSN: 2050-7488

The redox flow battery (RFB) is a suitable option for electricity storage due to its high energy efficiency, scalability and relative safety. However, the limited metallic resources for redox materials and the high cost in systems such as the all-vanadium RFB are major challenges for wider application. Organics may be sourced more abundantly and have lower prices than metal based redox couples. In this work a regenerative fuel cell involving relatively inexpensive organic redox couples is demonstrated. The electrochemical properties of 1,2-dihydrobenzoquinone-3,5-disulfonic acid (BQDS) are characterised by cyclic voltammetry and linear-sweep voltammetry under hydrodynamic conditions. A regenerative fuel cell using 0.65 M BQDS in 1 M H2SO4 as positive electrolyte and gaseous hydrogen (1 bar) as negative redox-material results in an open circuit cell voltage of 0.86 V, a power density of 122 mW/cm2, and an energy density of 10.90 Wh L-1 without considering the volume occupied by the hydrogen. Very promising performance with an energy efficiency >60% at 100 mA cm-2 for 200 cycles is reported. New organic redox species resistant to side reactions could facilitate the use of this new system in practical applications. The use of hydrogen may also contribute to reduced side reactions of the organic redox associated with degradation in the presence of oxygen.

Journal article

Parra-Puerto A, Ng KL, Fahy K, Goode AE, Ryan MP, Kucernak Aet al., 2019, Supported transition metal phosphides: Activity survey for HER, ORR, OER and corrosion resistance in acid and alkaline electrolytes, ACS Catalysis, Vol: 9, Pages: 11515-11529, ISSN: 2155-5435

Carbon supported MxPy (M = Ni, Co, W, Cr and Mo) were prepared via pyrolysis using a very simple and scalable method utilizing non-toxic metal and phosphorous precursors. The electrochemical hydrogen evolution (HER), oxygen reduction (ORR), and oxygen evolution (OER) reactions and corrosion resistance under both acid and alkaline conditions were examined for all these catalysts and compared to the benchmark catalysts Pt/C (HER/ORR) and IrO2(OER). The highest activities were found in alkaline solutions for Co2P for HER and ORR and Ni2P for OER. Good activity for these was also found in acid for some of these reactions, although the catalysts suffered from susceptibility to corrosion. Co2P was further studied in an alkaline environment as it shows high catalytic activity towards the oxygen reduction reaction (ORR) without significant hysteresis. The onset potential (at 0.5 mA cm-2) obtained was 0.8 V and a Tafel slope value of 38 mV dec-1 with a maximum kinetic mass activity of 2870 A gCo-1 at 0.7 V (RHE). Utilising high resolution transmission electron microscopy (HRTEM) it is possible to observe high-surface area needle-like single crystal cobalt oxide structures on the surfaces of the Co2P particles at the beginning of the ORR. Hence the high rates of initial corrosion of the Co2P identified appear to be associated with the dissolution and precipitation of Cobalt oxide on the particle surface. The as-synthesised Co2P/C also shows good performance in an 8-hour stability test for the Oxygen Evolution Reaction (OER), carried out at 1.6 V vs. RHE in alkaline conditions, with negligible drop in current density over time. Interestingly, in an acidic environment the catalyst is very active towards 2-electron- oxygen reduction leading to H2O2 with high selectivity (85%). It is intriguing that the pH dependence on this catalyst towards the ORR is similar to that seen for gold.

Journal article

Lopes T, Beruski O, Manthanwar A, Korkischko I, Pugliesi R, Stanojev M, Andrade M, Pistikopoulos E, Perez J, Fonseca R, Meneghini R, Kucernak Aet al., 2019, Spatially resolved oxygen reaction, water, and temperature distribution: Experimental results as a function of flow field and implications for polymer electrolyte fuel cell operation, Applied Energy, Vol: 252, ISSN: 0306-2619

In situ and ex situ spatially-resolved techniques are employed to investigate reactant distribution and its impacts in a polymer electrolyte fuel cell. Temperature distribution data provides further evidence for secondary flows inferred from reactant imaging data, highlighting the contribution of convection in heat as well as reactant distribution. Water build-up from neutron tomography is linked to component degradation, matching the pattern seen in the reactant distribution and thus suggesting that high, non-uniform local current densities shape degradation patterns in fuel cells. The correlations shown between different techniques confirm the use of the versatile reactant imaging technique, which is used to compare commonly used flow field designs. Among serpentine-type designs, the single serpentine is superior in both equivalent current density and reactant distribution, showing large contributions from convective flow. On the other hand, the interdigitated design is shown to produce larger equivalent current densities, while showing a somewhat poorer reactant distribution. Considering the correlations drawn between the techniques, this suggests that the interdigitated design compromises durability in favour of power output. The results highlight how established techniques provide a robust background for the use of a new and flexible imaging technique toward designing advanced flow fields for practical fuel cell applications.

Journal article

Anthony D, Nguyen S, Senokos E, Bismarck A, Kucernak A, Greenhalgh E, Shaffer Met al., 2019, Hierarchical carbon aerogel modified carbon fiber composites for structural power applications, 22nd International Conference on Composite Materials 2019 (ICCM22), Publisher: Engineers Australia, Pages: 1-7

The desire to reduce overall weight in devices is a key driver for perpetual material development; the ability to combine composites with energy storage functions/capabilities which simultaneously provide structural integrity has the potential to supersede monofunctional components. To achieve this ambition, the multifunctional structure must perform both mechanical and energy storage functions sufficiently, but often there is a trade off in performance which is a significant challenge to overcome. Carbon aerogels have been shown to contribute positively to (electro-chemical double layer) capacitive performance due to an increased surface area in multifunctional carbon fiber based composite electrodes, but have also been shown to reduce mechanical properties; the addition of nanoscale reinforcers, such as carbon nanotubes, graphene or alike, with their superlative electrical and mechanical properties are proposed to address these concerns and create a truly hierarchical structure suitable for structural power applications.

Conference paper

Montelongo Y, Sikdar D, Ma Y, McIntosh AJS, Velleman L, Kucernak AR, Edel JB, Kornyshev AAet al., 2019, Author Correction: Electrotunable nanoplasmonic liquid mirror., Nat Mater, ISSN: 1476-1122

In the version of this Article originally published, the last sentence of the acknowledgements incorrectly read 'L.V. acknowledges the support of a Marie Skodowska-Curie fellowship (N-SHEAD)'; it should have read 'L.V. and D.S. acknowledge the support of Marie Skłodowska-Curie fellowships, N-SHEAD and S-OMMs, respectively'.

Journal article

Sikdar D, Ma Y, Kucernak AR, Edel JB, Kornyshev AAet al., 2019, Nanoplasmonic metamaterial devices as electrically switchable perfect mirrors and perfect absorbers, Conference on Lasers and Electro-Optics (CLEO), Publisher: IEEE, Pages: 1-2, ISSN: 2160-9020

We introduce nanoplasmonic metamaterial devices — electrically-switchable between perfect- mirror/absorber states — based on voltage-controlled assembly/disassembly of gold nanoparticles on silver films. These are investigated using effective-medium-theory, verified with simulations and experiments.

Conference paper

Sikdar D, Ma Y, Kucernak AR, Edel JB, Kornyshev AAet al., 2019, Nanoplasmonic Metamaterial Devices as Electrically Switchable Perfect Mirrors and Perfect Absorbers

© 2019 The Author(s) 2019 OSA. We introduce nanoplasmonic metamaterial devices - electrically-switchable between perfect-mirror/absorber states - based on voltage-controlled assembly/disassembly of gold nanoparticles on silver films. These are investigated using effective-medium-theory, verified with simulations and experiments.

Conference paper

Castanheira L, Bedouet M, Kucernak A, Hinds Get al., 2019, Influence of microporous layer on corrosion of metallic bipolar plates in fuel cells, Journal of Power Sources, Vol: 418, Pages: 147-151, ISSN: 0378-7753

The effect of the presence of a microporous layer on the propensity for corrosion of metallic bipolar plates in an operating polymer electrolyte membrane fuel cell is investigated using an in situ reference electrode array. The local potential at the surface of the cathode bipolar plate is significantly more negative in the presence of the microporous layer, which is attributed to the higher ionic resistance of the aqueous phase in the reactant transport layer associated with more effective removal of water from the catalyst layer/reactant transport layer interface. As a result the bipolar plate is effectively shielded from elevated potentials that may be present at the cathode electrode, even during start-up and shutdown of the cell. Revision of ex situ test protocols for candidate bipolar plate materials, surface treatments and coatings is recommended to reduce unnecessary conservatism in testing.

Journal article

Malko D, Guo Y, Jones P, Britovsek G, Kucernak Aet al., 2019, Heterogeneous iron containing carbon catalyst (Fe-N/C) for epoxidation with molecular oxygen, Journal of Catalysis, Vol: 370, Pages: 357-363, ISSN: 0021-9517

Pyrolized transition metal and nitrogen containing carbon materials (M-N/C) have shown promising activities as electrocatalysts for oxygen reduction reactions (ORR) in fuel cell cathodes. Similar materials have recently gained interest as heterogeneous catalysts. We report that ORR-active heterogeneous M-N/C materials can catalyze the chemical epoxidation of olefins with molecular oxygen and two equivalents of aldehyde at room temperature and ambient pressure. The observed yield and selectivity is higher than that for homogeneous analogues and the catalysts achieve TOF > 2700 h−1 and TON > 16,000. The ability to recycle the catalyst several times is also demonstrated.

Journal article

Rubio-Garcia J, Kucernak A, Zhao D, Lei D, Fahy K, Yufit V, Brandon N, Gomez-Gonzalez Met al., 2019, Hydrogen/manganese hybrid redox flow battery, JPhys Energy, Vol: 1, ISSN: 2515-7655

Electrochemical energy storage is a key enabling technology for further integration of renewables sources. Redox flow batteries (RFBs) are promising candidates for such applications as a result of their durability, efficiency and fast response. However, deployment of existing RFBs is hindered by the relatively high cost of the (typically vanadium-based) electrolyte. Manganese is an earth-abundant and inexpensive element that is widely used in disposable alkaline batteries. However it has hitherto been little explored for RFBs due to the instability of Mn(III) leading to precipitation of MnO2 via a disproportionation reaction. Here we show that by combining the facile hydrogen negative electrode reaction with electrolytes that suppress Mn(III) disproportionation, it is possible to construct a hydrogen/manganese hybrid RFB with high round trip energy efficiency (82%), and high power and energy density (1410 mW cm−2, 33 Wh l−1), at an estimated 70% cost reduction compared to vanadium redox flow batteries.

Journal article

Ma Y, Zagar C, Klemme DJ, Sikdar D, Velleman L, Montelongo Y, Oh SH, Kucernak AR, Edel JB, Kornyshev AAet al., 2018, A tunable nanoplasmonic mirror at an electrochemical interface, ACS Photonics, Vol: 5, Pages: 4604-4616, ISSN: 2330-4022

Designing tunable optical metamaterials is one of the great challenges in photonics. Strategies for reversible tuning of nanoengineered devices are currently being sought through electromagnetic or piezo effects. For example, bottom-up self-assembly of nanoparticles at solid | liquid or liquid | liquid interfaces can be used to tune optical responses by varying their structure either chemically or through applied voltage. Here, we report on a fully reversible tunable-color mirror based on a TiN-coated Ag substrate immersed in an aqueous solution of negatively charged Au-nanoparticles (NPs). Switching electrode potential can be used to fully control the assembly/disassembly of NPs at the electrode | electrolyte interface within a 0.6 V wide electrochemical window. The plasmon coupling between the electrode and the adsorbed NP array at high positive potentials produces a dip in the optical reflectance spectrum, creating the "absorber" state. Desorption of NPs at low potentials eliminates the dip, returning the system to the reflective "mirror" state. The intensity and wavelength of the dip can be finely tuned through electrode-potential and electrolyte concentration. The excellent match between the experimental data and the theory of optical response for such system allows us to extract valuable information on equilibrium and kinetic properties of NP-assembly/disassembly. Together with modeling of the latter, this study promotes optimization of such meta-surfaces for building electrotunable reflector devices.

Journal article

Tariq F, Rubio-Garcia J, Yufit V, Bertei A, Chakrabarti BK, Kucernak A, Brandon Net al., 2018, Uncovering the mechanisms of electrolyte permeation in porous electrodes for redox flow batteries through real time in situ 3D imaging, SUSTAINABLE ENERGY & FUELS, Vol: 2, Pages: 2068-2080, ISSN: 2398-4902

Journal article

Riedel R, Malko D, Seel A, Choi H, Porch A, Edwards P, Barrett A, Kucernak Aet al., 2018, Ion pairing and stability of alkalides in organic solutions, 256th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nanoscience, Nanotechnology and Beyond, Publisher: AMER CHEMICAL SOC, ISSN: 0065-7727

Conference paper

Rubio-Garcia J, Kucernak ARJ, Charleson A, 2018, Direct visualization of reactant transport in forced convection electrochemical cells and its application to Redox Flow Batteries, Electrochemistry Communications, Vol: 93, Pages: 128-132, ISSN: 1388-2481

A novel, simple and low cost electrochemiluminescence imaging method for monitoring mass transport phenomena in a redox flow battery-like system is presented. Luminol solutions were pumped through a flow field (FF) with a given design. At the flowfield/electrode interface light is emitted upon dye oxidation allowing direct visualization of channels, U-bends and regions of poor wetting. Image analysis allows direct visualization of reactant distribution and poor mass transport through tortuous materials. These results were compared with the experimental performance of an all‑vanadium redox flow battery with different FFs as a function of flow and good correlation achieved.

Journal article

Jackson C, Smith GT, Markiewicz M, Inwood DW, Leach AS, Whalley PS, Kucernak AR, Russell AE, Kramer D, Levecque PBJet al., 2018, Support induced charge transfer effects on electrochemical characteristics of Pt nanoparticle electrocatalysts, Journal of Electroanalytical Chemistry, Vol: 819, Pages: 163-170, ISSN: 1572-6657

The electrokinetic properties of Pt nanoparticles supported on Carbon (Pt/C) and Boron Carbide-Graphite composite (Pt/BC) are compared over a wide potential range. The influence of the support on the electronic state of Pt was investigated via in-situ X-ray Absorption Spectroscopy. Pt d-band filling, determined from XANES white line analysis, was lower and nearly constant between 0.4 and 0.95V vs. RHE for Pt/BC, indicating more positively charged particles in the double layer region and a delay in the onset of oxide formation by about 0.2V compared to the Pt/C catalyst, which showed a marked increase in d-band vacancies above 0.8V vs. RHE. Moreover, δμ analysis of the XANES data indicated a lack of sub-surface oxygen for the Pt/BC catalyst compared to the Pt/C catalyst above 0.9V vs. RHE. Additional anion adsorption on the Pt/BC in the double layer region, detected by CO displacement, was also confirmed by XANES analysis of the d-band occupancy. The H 2 oxidation activities of electrodes with low catalyst loadings were assessed under high mass transport conditions using the floating electrode methodology. The metal-support interaction between the Pt and BC support improved the maximum hydrogen oxidation current density by 1.4 times when compared to Pt/C.

Journal article

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